JPH0242070A - 1, 2, 3-benzothiazole-4-carboxylic acid derivative as plant growth regulator - Google Patents

Abstract

NEW MATERIAL: A compd. of formula I [wherein X is H, a halogen, a 1-3C alkyl and alkoxy and a 1-3C alkylthio; A is -OR (wherein R is H, a metal, ammonium cation, an alkyl, an aryl, etc.), -SR, formula IV (wherein R¹, R² are each H, a 1-16C alkyl, cyano, phenyl, etc., and R¹ and R² together form a 3-7C heterocyclic or carbon ring)].

EXAMPLE: 5-Chloro-1,2,3-benzothiadiazole-4-carboxylic acid benzyl ester.

USE: An effective ingredient for a plant growth controller. Growth of plants among crops such as sugar canes, grains, corns, fruits, rices, soybeans or coated crops is controlled, especially suppressed.

PROCESS: A new 1,2,3,-benzothiadiazole-4-carboxylic acid halide of formula II (wherein Hal is halogen) is reacted with an alcohol, a thiol or an oxime of formula II in an inert solvent in the presence of a base to obtain the compd. of the formula I.

COPYRIGHT: (C)1990,JPO

Description

[Detailed description of the invention] Industrial application field> The present invention provides novel 1,2,5-benzothiadiazole-4-
Substitution 1 represented by the following formula (■) on the carboxylic acid derivative,
The present invention relates to a plant growth regulating composition containing a 2.3-benzothiadiazole-4-carboxylic acid derivative as an active ingredient.

The present invention further discloses all methods for preparing these compositions and active compounds.

The invention also relates to a method for regulating, in particular inhibiting, plant growth by using the active compounds or compositions containing them.

<Means for solving problems/problems to be solved by conventional techniques/inventions> The present 1,2,5-benzothiadiazole-4-carboxylic acid derivative has the following formula ■ COA [wherein, X is a hydrogen atom, represents a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or an alkylthio group having 1 to 3 carbon atoms, and A is a group -OR, -5R or -0N=C(R1 ) R goose t-
R is a hydrogen atom, a metal or ammonium cation, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group or an aryl group (which may be unsubstituted or substituted), a heterocyclic group or a monosaccharide group t-
R1 and R2 are each independently a hydrogen atom, a C1-C16 alkyl group, a C2-C8
represents an alkoxyalkyl group, a cyano group, an unsubstituted or substituted phenyl group, or a substituted or unsubstituted alkanoyl or alkenoyl group, and R1 and R1 together with the carbon atoms bonded to them represent 3 to 3 in the ring. A heterocyclic ring having 7JQ molecules or carbon IRt-]

In these definitions, R, R, and R2 have the following meanings: R is a hydrogen atom, an alkali metal, an alkaline earth metal, aluminum, copper, nickel, manganese, zinc, iron or steel ion; basic group (where R4 is independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms) represents a halogenoalkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a pyridyl group, and the two R4 together represent a group having 3 to 6 carbon atoms interrupted by an oxygen atom. (can also form an alkylene group of 7), R represents an alkyl group having 1 to 8 carbon atoms; a halogen atom, a cyano group, a nitro group, a hydroxy group, (T)Co C1-C4 alkyl group, (T)-Coon or (T)-Coo-C1-C8 alkyl group substituted with C1-C4 alkyl group; C3-C8 alkyl group 6 alkenyl group, halogen-substituted C3-C6 alkenyl group, C3-C6 alkenyl group
an alkynyl group, a halogen-substituted alkynyl group having 3 to 6 carbon atoms, (T)n-cycloalkyl group having 3 to 8 carbon atoms, or the following formula %): (In each formula, W is unsubstituted or 0 substituted with a halogen atom, a trifluoromethyl group, a cyano group, an alkyl group having 1 or 2 carbon atoms or an alkoxycarbonyl group having 1 or 2 carbon atoms - an alkyleneimino group having 2 to 4 carbon atoms
, N and a 5- to 7-membered saturated or unsaturated heterocycle having 1 to 5 heteroatoms from group 8 or a monosaccharide group, T is a straight-chain or branched chain having 1 to 8 carbon atoms; alkylene group, especially K -CH鵞--CH, CH, --CHICHx
CH* --CH(CHs)- or --C(CH,)CH
3-1 also represents an alkenylene group having 3 to 6 carbon atoms or an alkene group having 5 to 6 carbon atoms, T is also interrupted by an oxygen atom or CO, and optionally a cyclogen atom, It can also be substituted with hydroxy, C1-C5 alkyl, C1- or C2-halogenoalkyl, cyano or C0OH, and T is also the moiety y! of the cycloalkyl group. ! : n represents zero or 1, and R1 and R2 together with the carbon atoms bonded to n represent a heterocycle W or carbon having 3 to 7 atoms in the ring. 'R is formed, and Y and 2 are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a halogenoalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom having 1 to 4 carbon atoms; 1 to 4 halogenoalkoxy group, cyan group, nitro group, C1 to C4 alkoxycarbonyl group, or C1 to C4 alkylcarbonyl group, R3 is a hydrogen atom or a C1 to C4 alkyl group; and U represents an oxygen atom or a sulfur atom.

Compounds of the invention where A=OR include salts of carboxylic acids with primary, secondary and tertiary amines and with metal and ammonium ions.

The halogen atom itself or as a constituent of other substituents is a fluorine atom, chlorine atom, bromine atom or iodine atom, preferably a fluorine atom, chlorine atom or bromine atom, as itself or a constituent of another substituent. An alkyl group is to be understood as meaning a straight-chain or branched alkyl group. Depending on the number of carbon atoms indicated, they may include, for example, the following groups: methyl, ethyl and propyl, such as isopropyl, isobutyl, tert-butyl, nibutyl or impentyl. , butyl group, pentyl group, hexyl group, heptyl group or octyl group.

Alkenyl groups are, for example, propen-1-yl, allyl, buten-1-yl, buten-2-yl or buten-3-yl groups, which have several double bonds in their width. Examples of the alkynyl group include a propyl-2-yl group, a butyn-1-yl group, a butyn-2-yl group, a pentyn-4-yl group, and acyl and propargyl groups are preferred.

Suitable bases are, for example, inorganic and organic bases such as alkali metal and alkaline earth metal hydroxides, carbonates and bicarbonates, LiOH%NaOH1KOHMg
(OH)z or Ca(OH)z2 and also NaHCO
3, KHC03, Nag(Co)3 and CO, are preferred.

Examples of salt-forming amines include nitrimethylamine, triethylamine, tripropylamine, tributylamine, tribenzylamine, tricyclohexylamine, triamylamine, trihexylamine, N,N-dimethylaniline, N, N-dimethyltoluidine, N,N-dimethyl-p-aminopyridine, N-
Methylpyrrolidine, N-methylpiperidine, N-methylpyrrolidine, N-methylimidazole, N-methylvirol, N-methylmorpholine, N-methylhexamethyleneimine, pyridine, quinoline, α-picoline, inquinoline, pyrimidine, acridine, N, N, N
', N'-tetramethylethylenediamine, N, N
, N',N'-tetraethylethylenediamine, quinoxaline, N-7'' lobildiimbrobylamine, N,N
-dimethylcyclohexylamine, 2,6-lutidine,
2. Heterocyclic amines of the 4-lutidine, triethylenediamine and morpholine types.

Heterocycles are to be understood as, for example: furan, tetrahydrofuran, thiophene, tetrahydrofuran, virol, pyrrolidine, imidazole, 1
, 2.4-triazole, piperidine, pyridine, pyrimidine, morpholine or azacyclohebutane. In particular: furan-2-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl,
Tetrahydrobilan-2-yl group, 1,3-dioxolan-5-yl group, virol-1-(ru group, virol-2
-yl group, pyrrolidin-1-yl group, isoxazole-
3-yl group, isoxazol-4-yl group, 1,2-dithiazolin-5-yl group, imidazol-1-yl group,
1,2.4-) lyazol-1-yl group, 1,3.4-
) lyazol-1-yl group, thiophen-2-yl group,
piperidin-1-yl group, piperidin-4-yl group, pyridin-2-yl group, pyridin-3-yl group, pyridin-4-yl group, pyrimidin-2-yl group, pyrimidin-
4-yl group, pyrimidin-5-yl group, morpholine-1
-yl group or azacyclohebutan-1-yl group.

Monosaccharide groups are, for example, glucofuranosyl, galactopyranosyl, allofuranosyl or maethyl groups, the OH group of which is free or acetylated or esterified with a methyl, benzyl or impropyridenyl group. It should be understood that the Among the above groups, diisopropylidenyl derivatives are preferred, but apart from these groups, the following groups are particularly preferred: diacetone-D-glucosidyl group, 1.2,3.4-di0-
Inglopyriden-D-galactopyranos-6-yl group, 1,2,5.6-di-0-y7prohyriten-D-mannit-3-yl group, 1,2,5.6-di-O-inpropylyl group Den, D-allofuranocy-3-yl group, D-glucofuranocy-3-yl group, D-galactobira/cy 6
-yl group, D-mannit-3-1yl group, D-allofuranos-4-yl group, mannopyranosy-1-yl group, 2-
Methyl-〇-glucosidi-6-yl group, 1,2,5.
6-titraacetyl-D-galactopyranos-3-yl group and 2,S,5-)ribenzylribofuranos-1-yl group.

Because of their pronounced plant growth-regulating properties, especially inhibitory properties, active compounds having in their structure the following substituents or combinations of substituents are preferred: represents an alkoxy group having 1 to 3 atoms or an alkylthio group having 1 to 3 carbon atoms, A represents a group -OR, -5R or -0N=C(R,)R mushroom, R is a hydrogen atom, an alkali metal Cation, alkyl group having 1 to 8 carbon atoms, alkenyl group having 5 or 4 carbon atoms, alkynyl group having 3 to 4 carbon atoms, cycloalkyl group having 3 to 6 carbon atoms, phenyl group or benzyl group ( Phenyl ring is an alkyl group having 1 to 3 carbon atoms, a logenoalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms.
to 3 alkylthio groups, cyano groups, halogen atoms,
R8 and R1 each independently represent an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, or R1 and R2 together represent a 2- to 6-membered alkylene or alkenylene chain] j, 2. S-Benzothiadiazole derivative.

Compounds represented by the following formula 1a OOR [wherein X and R represent the above meanings], especially 1,2,3-benzothiadiazole-4-carboxylic acid methyl ester, 5-ri-a-1,2,3 -Benzothiadiazole-4-
Carboxylic acid methyl ester, 5-lyry-1,2,5-benzothiacyazole-4
-carboxylic acid, 5-chloro-1,2,3-benzothiacyazole-4-
Force/I/ phonic acid ethyl ester 5-chloro-1,2,
5-Pentzthiadiazole-4-carboxylic acid benzyl ester 5-methoxy-1*2*s-benzothiadiazole-4
-carboxylic acid methyl ester, 5-methylthio-1,2
, 3-penzthiadiazole-4-carboxylic acid methyl ester, 5-po o -1, 2, 3-benzothiadiazole-4, /J Luponryo n-butyl ester, 5
-Chloro-1,2,3-benzothiacyaso &-4. Q
Rubonic acid phenyl ester, 5-chloro-1,2,3-
Benzothiadiazole-4-carboxylic acid (2-chlorophenyl) ester 5-chloro-j, 2,3-benzothiacyazole-4-
Carboxylic acid propynyl ester, 5-chloro-1,2,
3-Benzothiasiasol-4-carboxylic acid (trimethylsilylethyl) ester, 5-chloro-1,2,3-benzothiadiazole-4-
Carboxylic acid (dimethoxyphosphonylethyl) ester,
and 5-chloro-1e 2 ,5-benzothiacyazole-
Potassium salt of 4-carboxylic acid.

1,2,3-benzothiadiazole-4-carboxylic acid thiol ester represented by the following formula 1b O5R [wherein X and R represent the above meanings], especially 1°2,3-benzothiadiazole-4-carboxylic acid thiol ester acid benzylthiol ester, 5-chloro-1,2,3-benzothiacyazole-4-
Force A/Fonic acid methylthiol ester, 5-methylthio-1,2,3-benzothiadiazole-4-carboxylic acid methylthiol ester, and 5-chloro-1,2,3-benzothiadiazole-4-
Carboxylic acid (methoxycarbonylmethylthiol ester.

1,2,3-benzothiadiazole-4-carboxylic acid oxime ester, especially 5-chloro -1,2,3-benzothiacyazole-4-carboxylic acid acetoxime ester.

1,2,3-benzothiadiazole- represented by formula l
4-carboxylic acid derivatives are new.

West German Patent Application DE-AI, 695,786 and French Patent No. 1,541,415 describe 1,2,3-benzothiadiazole as a biocidal active ingredient for use in herbicidal, insecticidal and fungicidal compositions. types are generally disclosed. None of the compounds included under formula 1 of the present invention are disclosed therein, nor are they known to have plant growth regulating activity. 1,2
．． 5-Benzothiadiazole-7-carboxylic acid is L Chem, 5oc-(C) 19, excluding biological properties.
7t, page 3991.

1.2.3-Benzothiadiazole-4-carboxylic acid derivatives are produced by the following method known per se.

II 1,2,3-benzothiadiazole-4- represented by 1 Nita
A carboxylic acid halide is reacted with an alcohol, thiol or oxime H-A in an inert organic solvent in the presence of a base. Reactivity H-A is R-OH, R-5H or H-0-N
The reaction where =C(R+)Rg is carried out with or without the addition of 4-alkylaminopyridine as catalyst.

1, 2j represented by 1m representing the alkyl group of 6
The -benzothiadiazole-4-carboxylic acid ester, the acid of formula If and the acid I-lide of formula n can be developed by known methods, such as the synthetic steps depicted below.

f 1,2,5-benzothiadiazole-4-carboxylic acid represented by the formula If is converted into an alcohol, thiol or oxime I (- Esterified or condensed with A.

In this reaction, in the presence of an acid such as -r-H-At4, sulfuric acid, hydrochloric acid, para-toluenesulfonic acid, or in the presence of boron trifluoride diethyl ether complex or dicyclohexylcarbodiimide, at -180°C, It is preferably used in the temperature range from 0° to 140° C., either in excess or in an inert organic solvent.

In the formula of 0HaL, where R is substituted or unsubstituted and has 1 carbon atom, E is, for example, a hydrogen atom, an unsubstituted or substituted group such as a methyl group, an ethyl group, an isopropyl group, a dodecyl group, etc. It represents an easily separated group such as an alkyl group having 1 to 12 carbon atoms or a benzyl group.

HaL is a halogen atom, preferably a chlorine atom or a bromine atom, R and X are the formula! represents the meaning defined in

In the above reaction, R preferably has 1 to 6 carbon atoms, optionally substituted with a rogen atom or a diphenyl group.
represents an alkyl group.

The 3-/) logno-2-nitrobenzoic acid represented by 2 is esterified by conventional methods, for example the ester of the formula V is esterified with an excess of alcohol R-OH in the presence of a small amount of sulfuric acid. It is then condensed with mercaptan 15-E in an inert organic solvent in the presence of an equimolar amount of base. The resulting 3-mercapto-2-nitrobenzoic acid ester represented by the formula ■ is then treated with a reducing agent to give the 2-mercapto-2-nitrobenzoic acid ester represented by the formula ■.
-reduced to amino-3-mercaptobenzoic acid. Treatment with nitrite (e.g. nitrous acid) results in ring closure and 1,2°3-penzthiasiasol-4 of formula I.
-carboxylic acid ester, which can be saponified in conventional manner to 1,2,3-benzothiacyazole-4-carboxylic acid of the formula If. This can be further converted to the 1,2,3-benzothiadiazole-4-carboxylic acid/)lide of formula (1) with a genifying agent such as thionyl chloride, phosphoryl chloride or the corresponding bromide.

The cyclization of the compound represented by the formula (3), in which E represents a hydrogen atom, a methyl group, an ethyl group, or a benzyl group, is carried out by diazotization with a nitrous acid compound at a temperature of -20° to 30°C in an acid catalyst. .

In this process, the acidic reaction medium used can be an aqueous dilution of an inorganic acid, such as, for example, hydrohalic acid, phosphoric acid, sulfuric acid or fluoroboric acid, but it is also possible to use suitable organic acids. It is. Suitable nitrite salts are both inorganic nitrite compounds such as alkali metal and alkaline earth metal salts and organic nitrite compounds such as alkyl nitrites.

The above-mentioned closed-field method is a method by which fused thiadiazole compounds can be obtained in an advantageous manner because E is an unsubstituted or substituted C1-C12 alkyl group (A, Buraway et al., J. Chem, So
c, Vol. 90, No. 1954).

The compound represented by the formula V is a compound represented by 2H5-E (E represents, for example, an ethyl group, an ethyl group, an isopropyl group or a benzyl group), which can be changed into a compound represented by 2). The reaction is carried out in an inert organic solvent with equal amounts of a base such as an alkali metal carbonate such as Na1CO3 or Co1, or an alkaline earth metal carbonate such as M
g C03) or in the presence of a metal hydride (eg LiH).

The compound of formula 2 can also be prepared by starting from a salt of the compound of formula For example MgC0,) or in the presence of a metal hydride (e.g. NaH or Lid), formula)
1s-E (E is unsubstituted or substituted 1 to 12 carbon atoms
alkyl groups such as methyl, ethyl, isopropyl, dodecyl or benzyl) and an inert, preferably dipolar, aprotic solvent such as dimethyl sulfoxide, dimethylformamide or N-methyl -pyrrolidone and the resulting derivative is treated with an alkylating agent R-L, where L is a leaving group (l
eaving group), for example, a halogen atom, preferably a chlorine atom or a bromine atom, or -05O2R (R-
L can be, for example, dimethyl sulfate)] in a one-step batch operation.

The obtained 3-mercapto-2-nitrobenzoic acid ester represented by formula (2) is then subjected to catalytic reduction or metal reduction (me
2-amino-3-mercaptobenzoic acid represented by the formula (1).

For the catalytic reduction, Raney nickel and palladium, platinum or rhodium catalysts can be used, for example: the reduction can be carried out at normal or slightly elevated pressure and at temperatures from 0° to 150°C.

Suitable solvents are, for example, tetrahydrofuran or dioxane.

For example, iron/hydrochloric acid, iron/acetic acid, tin/hydrochloric acid, zinc/hydrochloric acid can be used as reducing agents for metal reduction. The return is 0
It can be carried out at temperatures between 120°C and 120°C. Water or alcohols such as methanol, ethanol, n-propanol, isoglopanol, and also tetrahydrofuran or dioxolane or mixtures thereof can be used as solvents for this reaction.

Compounds of formula 1, where E=H, also hydrolyze the corresponding amino-benzothiadiazole of formula can be obtained by (Organ
ic 5ynthesis, Co11. Volume 3 No. 7
(See page 6).

In the above structures, unless otherwise specified, bases are understood to be both inorganic and organic bases. These include inorganic bases such as hydroxides, bicarbonates, carbonates and hydrides of lithium, sodium, potassium, calcium and barium, and also alkali metal amides such as NaNH2 or alkali IJ17 tium compounds such as n-butyllithium. included. Examples of organic bases include: amines, especially tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tribenzylamine, tricyclohexylamine, triamylamine, trihexylamine, N, N-dimethyl, aniline, N, N-dimethyltoluidine, N, N-dimethyl-p-aminopyridine, N-methylpyrrolidine, N-methylpiperidine, N
-Methylpyrrolidine, N-methylimidazole, N-methylvirol, N-methylmorpholine, N-methylhexamethyleneimine, pyridine, quinoline, a-picoline, β-picoline, inquinoline, pyrimidine, acridine, N, N, N , N-tetramethylethylenediamine,
N,N,N,N-tetraethylethylenediamine, quinoxaline, N-probyldiinoprobylamine, N,N
-dimethylcyclohexylamine, 2,6-lutidine,
2.4-lutidine or triethylenediamine.

Examples of inert solvents that can be used according to the specific reaction conditions include: halogenated hydrocarbons, especially chlorinated hydrocarbons, such as tetrachloroethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, Chloronaphthalene, dichloronaphthalene, carbon tetrachloride, trichloroethane, trichloroethylene, pentachloroethane, difluorobenzene, 1,2-dichloroethane,
1.1-dichloroethane, 1.2-cis-dichloroethylene, chlorobenzene, fluorobenzene, fromobenzene, iodobenzene, dichlorobenzene, cyfuromobenzene, chlorotoluene and hydriclorobenzene: ethers, e.g., ttf ethylglobyl ether, methyl-th Tri-butyl ether% n-butyl ethyl ether, sea n
-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, phenetol, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, thioanisole, dichloroethyl ether, methyl cellosolve: alcohols such as methanol, ethanol, n- Cl hanol, isopropanol, n-7''ll/-A/, isobutanol: nitrated hydrocarbons such as nitromethane, nitroethane, nitrobenzene, chloronitrobenzene and o-nitrotoluene; nitriles such as acetonitrile, butyronitrile, imbutyro Nitriles, benzonitriles and m-chlorobenzonitrile: aliphatic or cycloaliphatic hydrocarbons, such as heptane, nonane, cymol, boiling range 70
° to 190 °C petroleum distillates, cyclohexane, methylcyclohexane, decalin, petroleum ether, hexane,
Ligroin, trimethylpentane, 2,3.3-trimethylpentane and octane: esters such as ethyl acetate, acetoacetate, isobutyl acetate; amides,
For example formamide, methylformamide, dimethylformamide; ketones such as acetone, methyl ethyl ketone, and also optionally water. Mixtures of the abovementioned solvents and diluents are also suitable.

The above production method is not new and is based on known synthetic methods that can be found in the following literature: "The Chemi
Try of Heterocyclic comp
oundswith Nitrogen and 5u
lfur or Nitrigen.

5ulfur and Oxygen (Chemistry of nitrogen and sulfur or heterocyclic compounds containing nitrogen, sulfur and oxygen)” Interscience:
f41s 2z-York 1952: Bee Kirby et al. CP, Kirby et al., J. Chem.
Soc, (c), p. 321 (1967) and vol.
Page 250 (1970) and Page 3994 (1971): French Patent Specification (FR-PS) No. 154141
Issue 5: J, Org, Chem, Volume 27, No. 467
5 pages (1942); West German Open Gazette (Germa
n Offenlegungsschriften)
No. 2400887 and 2504383; 5U-PS
400574 (Chemical Abstracts (Che)
m, Abstr, ) 80 (9) 47661
h).

Formula 1. The compounds represented by If, n and ■ are new, but some of the compounds represented by formulas ■, V and ■ are new. The novel compounds form part of the invention.

The active ingredient of formula I is usually CLO5 to 4k
It is used commercially at an application rate of p/ha, especially α1 to 1 kp/ba.

Compounds of formula I are plant growth regulators. Plant growth regulators are agronomically desirable substances that cause or cause biochemical and/or physiological and/or morphological changes in plants. Growth regulators have one or several activities which, according to current experience, depend on the time of application, the rate of application, the method of application and the climatic conditions. Plant growth regulators can inhibit vigorous growth. This activity can be applied to lawns, ornamental plants in flower gardens, orchards, slopes, stadiums or industrial parks.
There is also interest in suppressing side shoots in tano plants.
5 tacks) and the proviso in cultivated land leads to reduced plants. Similar agronomic effects can be achieved in planting rapeseed, sunflower, corn and other cultivated crops. By suppressing vigorous growth, the number of plants per unit area increases. Another use for growth regulators is the selective control of soil cover plants in plantations or crop fields with extensive rows of planted plants. By strongly inhibiting the growth of these soil cover crops without killing them, they can achieve beneficial agronomic effects, such as preventing soil erosion and nitrogen, without collaborating with the planted plants. It has the effect of fixing the ground and loosening the ground.

Plant growth regulators can be used either quantitatively (e.g. increasing latex flow in rubber plants) or qualitatively (increasing sugar content).
can improve crop yields.

For example, it is possible to suppress the dominant buds and promote the growth of side buds in ornamental plants, and to promote flower formation or fruit cutting (e.g., in fruit trees, in order to facilitate the harvesting of olives, to facilitate mechanical harvesting). fruit cutting). The ripening time can be matched with plant growth regulators, which can be accelerated or delayed (eg opening of cotton, ripening of tomatoes and bananas).

Plants can be made more tolerant to climatic stresses such as cold, cold or saline soils.

Defoliation of plants can be induced at specific times to ultimately enable mechanical harvesting in cultivation, for example of cotton, potatoes, carrots or grapes.

The compounds of formula I are used in neat form or as compositions, preferably with the auxiliaries customary in formulation technology, and can therefore be prepared by known methods, for example as emulsion stock solutions, directly sprayable or dilutable solutions, diluted emulsions, Irrigation agent, water solvent,
It is formulated into powders, granules, and encapsulates, eg, with polymeric substances. Similar to the nature of the composition, spraying (sp
raying) s atomizing
The method of application, such as dusting, sprinkling or pouring, depends on the intended target and the environment of use.

The formulation, i.e. the composition containing the active ingredient of formula I and, if appropriate, solid or liquid additives, can be prepared by known methods.
For example, they are prepared by homogeneously mixing and/or milling the active ingredient with a solvent, a solid carrier and, if appropriate, extenders such as surface-active compounds (surfactants).

Suitable solvents are diaromatic hydrocarbons, preferably moieties having 8 to 12 carbon atoms, such as xylene mixtures or substituted naphthalenes; phthalates such as dibutyl phthalate or dioctyl phthalate, fatty acids such as cyclohexane or paraffins. group hydrocarbons, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide. A solvent and an epoxidized vegetable oil such as epoxidized coconut oil or soybean oil or water.

Solid carriers which can be used, for example in dusts and dispersible powders, are usually natural mineral fillers such as calcite, melk, kaolin, montmorillonite or attapulgite. It is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers to improve the physical properties. Suitable granulated absorbent carriers are of the porous type, e.g. pumice, crushed brick,
Seviolite or bentonite: and suitable non-absorbent carriers are materials such as calcite or sand. A large number of pre-granulated mineral and organic materials can be used, especially dolomite or pulverized plant debris.

Depending on the nature of the compound of formula 1 to be formulated, suitable surface-active compounds are nonionic, cationic and/or anionic surfactants with good emulsifying, dispersing and wetting properties.

It is to be understood that the term "1 surfactant" also includes mixtures of surfactants.

Suitable anionic surfactants are both so-called water-soluble synthetic surface-active compounds and water-soluble soaps.

The soaps applied are alkali metal salts, alkaline earth metal salts, or unsubstituted or substituted ammonium salts of higher fatty acids (C1o-Co), such as oleic acid or stearic acid, or natural fatty acids obtained, for example, from coconut oil or tallow. A mixture of sodium or potassium salts. Fatty acid methyltaurate salts may also be used.

However, so-called synthetic surfactants, especially aliphatic sulfonates, aliphatic sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates, are frequently used in history.

Aliphatic sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or optionally substituted ammonium salts, and contain an alkyl group having from 8 to 22 carbon atoms and also the alkyl part of an acyl group. , for example the sodium or calcium salts of lignosulfonic acid, dodecyl sulfate or mixtures of fatty alcohol sulfates obtained from natural fatty acids. These compounds also include salts of sulfuric acid esters and salts of sulfonic acids of fatty alcohol ethylene oxide adducts.

The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty acid group containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid-formaldehyde condensation products.

Corresponding phosphates, such as salts of phosphoric acid esters of p-nonylphenol adducts containing 4 to 14 mol of ethylene oxide, and phospholipids are also suitable.

Nonionic surfactants are in particular polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols or saturated or unsaturated fatty acids and alkylphenols, which derivatives contain from 3 to 30 glycol ether groups, (aliphatic) 8 to 20 carbon atoms in the hydrocarbon portion and 6 to 18 carbon atoms in the alkyl portion of the alkylphenol.

Further suitable nonionic surfactants are water-soluble polyethylene oxide adducts, which together with polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycols having 1 to 10 carbon atoms in the alkyl chain 20 to 2
Contains 50 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Typical examples of nonionic surfactants are nonylphenol-polyethoxyethanol and castor oil polyglycol.
ether, polypropylene/polyethylene oxide adduct, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan triolate, are also suitable nonionic surfactants.

Cationic surfactants are used in particular with at least one C 8 -C 22 alkyl group as N-substituent and optionally with lower halogenated alkyl, benzyl or lower hydroxyalkyl groups as other substituents. It is a quaternary ammonium salt containing. The salt is preferably in the form of a halogenide, methyl sulfate or ethyl sulfate, for example stearyltrimethylammonium chloride or benzyl di(2-chloroethyl)ethylammonium bromide.

Surfactants customary in the pharmaceutical industry are described, for example, in the following publications: McCutchan's Detergents and Emulsifiers Annual (Me Cu
tcheon's Detergents and Em
ulsifiers Annual)', my
Publishers, Ringwood, New Jersey, 197
Year 9: Helmut Schettach x (Helmut 5
tache).

1 Tensid-Ta
Shenbuch)” (Handbook of Surf Actance), Karl, Hanserfurlag (C
arl Hanser Verlag), Mienchen and Vienna, f981.

Herbicidal and plant growth regulating preparations usually contain α of the active ingredient of formula I.
1 to 95%, especially α1 to 80%, solid or liquid additives F to 999%, and surfactants A to 25%, especially α, 1 to 25%.

Preferred formulations include, in particular, those consisting of the following components (the figures indicate percentages by weight): emulsion stock granules powder suspension stock commercial products are preferably in the form of m-floats, but the composition is not consumed. People usually use it diluted.

The formulation can be applied diluted to 1001% of the active ingredient.

The application rate is usually flo05 to 5kI! The effective production area is hectares.

The compositions may also contain other additives, such as stabilizers, antifoams, viscosity regulators, binders, tackifiers and fertilizers, or other active ingredients for special effects.

<Example - Effect of the invention> Irrigation agent production 15 to yu% OOCHs 2-Amino-3-benzylthio-6-chlorobenzoic acid methyl ester 5.7Of (LL0185 mol), concentrated hydrochloric acid 25- and water 11al? Stir the mixture thoroughly at room temperature. The mixture is then cooled to -10° C. and a solution of 1 jOf sodium nitrite in 51 °C of water is slowly added dropwise with stirring. A precipitate forms during this operation. The reaction mixture is stirred at 5° C. for 16 hours, then some hexane/ethyl acetate is added and the residue 1i-filtered.

The residue was washed with water and dried, melting point, 126-128
The title product 562 (85% of theoretical yield) was obtained at 50°C.

The necessary 2-amino-3-benzylthiobenzoic acid as starting material is obtained as follows: into a mixture of 81.6 f (1585 mol) of potassium carbonate in 2.5 d of 80% aqueous methanol with stirring at room temperature. Benzylmercaptan 64-(α544 mol) is added dropwise. During the next 2 hours, the 3-bromo-6
-Chloro-2-benzoic acid methyl ester 160t (α5
44 mol) is added. A yellow precipitate forms after a while. The reaction mixture is stirred at room temperature for 16 hours and then filtered. The precipitate was washed with water, partially dried, and then heated to 80°C.
% methanol. In this way, melting point 93
Title product at 10.degree. x5f (56% of theoretical yield) is obtained.

3-benzylthi, t-6-/chloro 2-nitrobenzoic acid methyl ester 1 & 9f (105 mol) is dissolved in tetrahydrofuran 170d and then hydrogenated in the presence of Raney nickel 152 at normal pressure and a temperature of 20 to 25°C. Added. Then, the catalyst 1' is removed and the p liquid is concentrated until it becomes an oil.

C00CR.

2-Amino-3-benzylthio-benzoic acid Mety-A/
In a well-stirred mixture of
Sodium nitrite (
Add the L25f solution slowly dropwise. The reaction mixture is stirred at room temperature for 2 hours, then poured onto ice/water and extracted with ethyl acetate.

The organic phase is washed with water, dried over magnesium sulphate, filtered and evaporated. The remaining crystal mass is crushed with hexane, filtered, and the resulting crystals are dried. Yield CLs
or (theoretical amount of 78 chi).

Melting point 95-96°C.

Benzyl alcohol 1.50? (α012 mol),
A solution of triethylamine t 50 f (α015 mol) and ethyl acetate 50 is cooled to 15°C.

1111 L of a solution of 1011 mol of 5-chloro-1,2,3benzothiadiazole-4-carboxylic acid chloride in ethyl acetate are then added with stirring, and the solution is stirred for a further 5 hours at room temperature. The reaction mixture is then poured onto ice/water and the aqueous phase is washed twice with ethyl acetate. The organic extracts are washed with water, dried over magnesium sulfate, filtered, and concentrated. The remaining oil is chromatographed on a small silica gel column using eluent (ethyl acetate/hexane).

After evaporation of the eluent, 2.92 g (87 g of theoretical yield) of the target compound with a melting point of 99 DEG-101 DEG C. remain.

5-chloro-1°2,3-benzothiadiazole used as starting material is prepared as follows: 5-chloro-1,2,3-benzothiadiazole-4-
A solution of 19.5 r (1085 mol) of carboxylic acid methyl ester was dissolved in 1651 Ll of total dioxane, 521 L of 2N aqueous sodium hydroxide solution was added, and 4
Stir for an hour. The solution was then allowed to cool and was diluted with 2N
Hydrochloric acid 52IE1! ! Add and pour over ice/water. A precipitate forms, which is filtered, washed with water and dried. In this way, 18 g of 5-chloro-1.2.5-benzothiadiazole-4-carboxylic acid (98% of theoretical yield) having a melting point of 211 DEG -212 DEG C. is obtained.

2-Amino-3-benzylmercapto-6-chloro-benzoic acid 11 (1 (α041 mol)) was prepared at Preparation #R55@7
and 25 txl of water and stirred for 30 minutes at Sa°C.The solution was then cooled to -5°C, and 2.0% of sodium nitrite in 10+wj of water was added thereto with slow stirring. A solution of 92(a, 042 mol) is added dropwise at a slow rate. The reaction mixture is stirred at the same temperature for 3 hours and then for a further 17 hours, during which time the temperature is allowed to rise to room temperature. A precipitate forms, which is filtered, washed with water and dried. Then it is triturated with hexane/ether, filtered again and dried. 5-chloro-1,2j-benzothiadiazole-4-carboxylic acid &22 (7ou of theoretical yield) is thus obtained.

Toluene (dried over Molecule sieve) 1
5-chloro-1,2,,5-benzothiadiazole-4-carboxylic acid 1α02 (α047 mol) is suspended in 000 mL followed by toluene 25al! 7,4 d (CL 102 mol) f thionyl chloride is continued to be added dropwise at 90° C. during the next hour. The reaction mixture is then stirred at the same temperature for 6 hours. The solvent is then removed in a rotary evaporator. The remaining oil is used for further reactions.

Ru.

The compounds in Tables 1 to 5 are prepared in the same manner as in these Examples. Degrees are in degrees Celsius.

Table 1 0OR 5-Rio1.2.3-Benzothiacyasole-4-
Carboxylic acid methyl ester"s, 5t (1024 mol)
, Methanol 50d and S) IJ Um Methylate S4
A solution of M methanol solution adm is heated under reflux for 48 hours. The reaction mixture is then poured onto ice/water and the resulting precipitate is filtered, washed with water, dried and recrystallized from hexane/ethyl acetate. The title compound 552 (70% of the theoretical yield) with a melting point of 93-94°C was obtained. ) Table 1 (continued) Table 1 (continued) Table 1 (continued) Table 1 (continued) CO5R 1st column (continued) Table 2 (continued) Table 3 (Intermediate) Table 3 (continued) ) Table 3 (Continued) Formulation Examples Example 5: Formulation Example of Active Ingredients in Formula % Formula % (Ch is Weight b) C) Active Ingredients in Tables 1 and 2 Sodium Lignosulfonate Sodium Lauryl Sulfate 60 5% α5% 5% Highly dispersed silicic acid 5% 27% 27% Kaolin 67% -59,5qb After thoroughly mixing the active ingredient with the auxiliary agent, the mixture is thoroughly ground in a suitable mill and diluted with water. By doing this, an aquarium can be obtained in which a suspension with a desired concentration can be obtained.

b) Emulsion stock solution a) b) d) Extruded granules 10 active ingredients listed in Tables 1 and 2 Calcium dodecylbenzenesulfonate 3dIb3
% Cyclohexanone 30% 10% Xylene mixture 50% 79% By diluting this emulsion stock solution with water, an emulsion of the desired concentration can be obtained.

C) Powders - a) b) Active ingredients from Tables 1 and 2 01% 1
% Talc 999% Kaolin
- A ready-to-use powder is obtained by mixing the 99% active ingredient with the carrier and milling the mixture in a suitable mill.

a) b) Active ingredients in Tables 1 and 2 10%
1% Sodium Lignosulfonate 2T 2T Carboxymethylcellulose
1chi 1% kaolin 87%
The 96% active ingredient is mixed and milled with the auxiliaries and the mixture is subsequently moistened with water. The mixture is extruded and dried in a stream of air.

e) Coated granules Active ingredients in Tables 1 and 2 3% polyethylene glycol 200 2% kaolin
94% finely ground active ingredients,
Apply evenly to the kaolin moistened with polyethylene glycol in a mixer. By this method, non-dusting coated granules are obtained.

f) M cloudy stock solution a) b) Active ingredients listed in Tables 1 and 2 40% 5
%Ethylene glycol 10% 10% Sodium lignosulfonate 1o%
5-carboxymethylcellulose 1%
1 yen 37 thiformaldehyde aqueous solution α
2% 0.24 water
By homogeneously mixing the finely ground active ingredient with auxiliaries and diluting with water, a suspendable concentrate is obtained which can be used to obtain a suspension of the desired concentration.

Psophocarpus palusullis (P 5ophocar
puspalus tris) and CF Centrosema pubescens.
cens), normal soil (45%), beet (45%
) and Zonolite (10%) in 4c1n beet pots.
Breed from ots). They are grown in a greenhouse with a day temperature of 27°C and a night temperature of 23°C. Exposure time was at least 14 hours/day at a minimum density of 7000 lux.

50 days after planting the shoots, transplant them into pots with a diameter of 13 sides. After another 60 days, cut them to a height of 15 strokes and add the substance to be tested to α6 to 6 y/h.
a and water at 2000 t/ha. The prosthesis is made by diluting 25% hydrating powder with water until the desired application concentration is reached. 4 weeks later,
New growth of treated plants was evaluated and compared to that of trimmed but untreated plants (normal growth of untreated control plants). Regeneration length is usually expressed by the length of growth. The compounds tested reduce regeneration length by 10 to 60 inches.

Example 7: Soybean growth inhibition Williams m soybeans were grown in normal soil (45%), beet (45%) and zonolite
The seeds are sown in earthenware pots filled with Zono 1ite (10%) and cultivated in a climatic chamber with a daytime temperature of 24°C and a nighttime temperature of 19°C. Exposure time was 16 hours/day at a density of approximately 350μ einstein.

After about 24 days, they were transplanted into 1851 pots, 2 plants per pot. Another 12 days after they reach the 6-5 leaf stage, a concentration of 10 to 20,017 h a of active ingredient and 2
Pros containing 00 t/ha of water was sprayed. The prosthesis is made from 25% hydrating powder which is diluted with water until the desired active ingredient is obtained.

Approximately 4 weeks after this application, the test is evaluated. New growth since application is measured and compared to that of untreated control plants (usually 1
00chi growth). The result is expressed in chi. The test compound inhibited new growth by 10 to 80%.

Example date: Grain growth suppression Iban summer barley containing sterilized soil
Sow in a plastic pot of 3, daytime temperature 10-15
The plants are grown in a greenhouse with a night temperature of 5-10°C. The exposure time was 155 hours per day at a density of 25,000 lux.

After about 34 days, thin the plants to 4 per pot and add the active substance α.
Sprayed with a prosthesis containing 3 to 5 Ky/ha and 500 z,'ha of water. The application prosthesis was made from 25% backing and diluted with water until the desired application concentration was reached. The plants are then placed in a greenhouse with a daytime humidity of at least 10° C. and a light exposure time of 155 hours per day. The test is 28 of processing.
will be evaluated after a day. Measure new growth and measure untreated plants (
Compared with that of normal growth), it is expressed in terms of chi for normal growth. Test compounds inhibited new growth for 10 to 80 seconds.

Claims (19)

[Claims] (1) The following formula I ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) [In the formula, X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. or represents an alkylthio group having 1 to 3 carbon atoms, A is a group -OR, -SR or -ON=C(R_1)R_2
represents a hydrogen atom, a metal or ammonium cation, an alkyl group, an alkenyl group, an alkynyl group,
represents a cycloalkyl group or an aryl group (which may be unsubstituted or substituted), a heterocyclic group or a monosaccharide group, R_1 and R_2 are each independently a hydrogen atom, a C 1 to C 16 represents an alkyl group, an alkoxyalkyl group having 2 to 8 carbon atoms, a cyano group, an unsubstituted or substituted phenyl group, or a substituted or unsubstituted alkanoyl or alkenoyl group, and R_1 and R_2 are the carbon atoms bonded to them; 1,2,3-benzothiadiazole-4- which together represents a heterocycle or carbocycle having 3 to 7 atoms in the ring.
Carboxylic acid derivative. (2) The following formula I ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) [In the formula, X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 or 2 carbon atoms. or represents an alkylthio group having 1 to 3 carbon atoms, A is a group -OR, -SR or -ON=C(R_1)R_2
R represents a hydrogen atom, an alkali metal, an alkaline earth metal, aluminum, copper, nickel, manganese, zinc, iron or silver cation, a basic group, or the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Formula Among them, R_4 are each independently a hydrogen atom, the number of carbon atoms is 1
alkyl group having 1 to 6 carbon atoms, hydroxyalkyl group having 1 to 6 carbon atoms, alkoxyalkyl group having 2 to 6 carbon atoms, halogenoalkyl group having 1 to 6 carbon atoms, alkenyl group having 3 to 6 carbon atoms, benzyl or a pyridyl group, and the two R_4 can also be taken together to form a C 3 -C 7 alkylene group interrupted by an oxygen atom), R further represents an ammonium cation of the form C1-C8 alkyl group; halogen atom, cyano group, nitro group, hydroxy group, (Y)CO-C1-C4 alkyl group, (
T)-COOH or (T)-COO-C1-C8 alkyl group substituted with C1-C4 alkyl group; C3-C6 alkenyl group, halogen-substituted C3-C3 alkyl group an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 3 to 6 carbon atoms, a halogen-substituted alkynyl group having 3 to 6 carbon atoms, a (T)_n-cycloalkyl group having 3 to 8 carbon atoms, or the following formula ▲ formula, There are chemical formulas, tables, etc. ▼, (T)_n-naphthyl-(Y), (T)_n-Si (C_1-C_8-alkyl group)_3
, (T)-NR_2R_3-, -N=C(R_1)R_
2;▲There are mathematical formulas, chemical formulas, tables, etc.▼(C_1-C_
4-alkyl group), ▲Mathematical formulas, chemical formulas, tables, etc.▼
and (T)_n-W; (in each formula, W is unsubstituted or a halogen atom, a trifluoromethyl group, a cyano group, an alkyl group having 1 or 2 carbon atoms, or an alkoxycarbonyl-carbon having 1 or 2 carbon atoms) represents a 5- to 7-membered saturated or unsaturated heterocycle having 1 to 3 heteroatoms from the group O, N and S substituted with an alkyleneimino group having 2 to 4 atoms, or represents a monosaccharide group, Y is a straight-chain or branched C1 -C8 alkylene group, in particular -CH_2-, -CH_2-CH
_2-, -CH_2CH_2CH_2-, -CH(CH
_3)- or -C(CH_3)CH_3-, furthermore C3 -C6 alkenylene or C3 -C6 alkynylene group, T is also interrupted by an oxygen atom or CO and optionally a halogen atom , hydroxy group, having 1 to 5 carbon atoms
can be substituted with an alkyl group, a halogenoalkyl group having 1 or 2 carbon atoms, a cyano group or a COOH group, T can also represent a moiety of a cycloalkyl group, n represents zero or 1, and R_1 and R_2 together with the carbon atoms bonded to them form a heterocycle W or carbocycle having 3 to 7 atoms in the ring, and Y and Z are hydrogen atoms, halogen atoms, carbon atoms Alkyl group of number 1 to 4, number of carbon atoms 1 to 4
a halogenoalkyl group, a C1-C4 alkoxy group, a C1-C4 halogenoalkoxy group, a cyano group, a nitro group, a C1-C4 alkoxycarbonyl group or a C1-C4 alkoxycarbonyl group 1 represents an alkylcarbonyl group, R_3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and U represents an oxygen atom or a sulfur atom) , 2,3-benzothiadiazole-4-carboxylic acid derivative. (3) The following formula I ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) [In the formula, X is a hydrogen atom, a halogen atom, an alkoxy group having 1 to 3 carbon atoms, or an alkylthio group having 1 to 3 carbon atoms. , A is a group -OR, -SR or -ON=C(R_1)R_2
R represents a hydrogen atom, an alkali metal cation, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 or 4 carbon atoms, an alkynyl group having 3 to 4 carbon atoms, or an alkynyl group having 3 to 6 carbon atoms. Cycloalkyl group, phenyl group or benzyl group (phenyl ring is an alkyl group having 1 to 3 carbon atoms, a halogenoalkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a 1 to 3 carbon atom group) (optionally substituted with an alkylthio group, cyano group, halogen atom, nitro group or methoxycarbonyl group), and R_1 and R_2 each independently have 1 to 6 carbon atoms.
represents an alkyl group having 2 to 6 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms, or R_1 and R_2 together represent 2
to 6-membered alkylene or alkenylene chain] A 1,2,3-benzothiadiazole derivative represented by: (4) The following formula I a ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I a) [In the formula, X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a represents an alkoxy group or an alkylthio group having 1 to 3 carbon atoms; R is a hydrogen atom, an alkali metal cation, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 or 4 carbon atoms, 3 or 4 carbon atoms; 4 alkynyl group, cycloalkyl group having 3 to 6 carbon atoms, phenyl group or benzyl group (phenyl ring is an alkyl group having 1 to 3 carbon atoms, halogenoalkyl group having 1 to 3 carbon atoms, 1 carbon atom) 1 to 3 alkoxy group, an alkylthio group having 1 to 3 carbon atoms, a cyano group, a halogen atom, a nitro group, or a methoxycarbonyl group] 1,2,3-benzothiadiazole represented by -4-
Carboxylic acid derivative. (5) 5-chloro-1,2,3-benzothiadiazole-4-carboxylic acid methyl ester, 5-chloro-1,2,3-benzothiadiazole-4-
Carboxylic acid, 5-chloro-1,2,3-benzothiadiazole-4-
Carboxylic acid ethyl ester, 5-chloro-1,2,3-benzothiadiazole-4-
Carboxylic acid benzyl ester, 5-methoxy-1,2,3-benzothiadiazole-4
-carboxylic acid methyl ester, 5-methylthio-1,2,3-benzothiadiazole-
4-carboxylic acid methyl ester, 5-chloro-1,2,
3-benzothiadiazole-4-carboxylic acid n-butyl ester, 5-chloro-1,2,3-benzothiadiazole-4-carboxylic acid phenyl ester, 5-chloro-1,2,3-benzothiadiazole-4-
Carboxylic acid (2-chlorophenyl) ester, 5-chloro-1,2,3-benzothiadiazole-4-
Carboxylic acid propynyl ester, 5-chloro-1,2,
3-benzothiadiazole-4-carboxylic acid (trimethylsilylethyl) ester, 5-chloro-1,2,3-benzothiadiazole-4-
Carboxylic acid (dimethoxyphosphonylethyl) ester,
and 5-chloro-1,2,3-benzothiadiazole-4-
5. The 1,2,3-benzothiadiazole-4-carboxylic acid derivative according to claim 4, which is selected from potassium salts of carboxylic acids. (6) The following formula I b ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I b) [In the formula, X is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or a represents an alkoxy group or an alkylthio group having 1 to 3 carbon atoms; R is a hydrogen atom, an alkali metal cation, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 or 4 carbon atoms, 3 or 4 carbon atoms; 4 alkynyl group, cycloalkyl group having 3 to 6 carbon atoms, phenyl group or benzyl group (phenyl nucleus is an alkyl group having 1 to 8 carbon atoms, halogenoalkyl group having 1 to 8 carbon atoms, 1 carbon atom) 1 to 8 alkoxy group, C1 to C8 alkylthio group, cyano group or nitro group]
Carboxylic acid thiol ester. (7) 5-chloro-1,2,3-benzothiadiazole-4-carboxylic acid benzylthiol ester, 5-chloro-1,2,3-benzothiadiazole-4-
Carboxylic acid methylthiol ester, 5-methylthio-1,2,3-benzothiadiazole-
4-carboxylic acid methylthiol ester, and 5-chloro-1,2,3-benzothiadiazole-4-
The 1,2,3-benzothiadiazole-4-carboxylic acid thiol ester according to claim 6, which is selected from carboxylic acids (methoxycarbonylmethylthiol esters). (8) The following formula I c ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I c) [In the formula, X is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or represents an alkylthio group having 1 to 3 carbon atoms, and R_1 and R_2 each independently have 1 to 6 carbon atoms;
represents an alkyl group, an alkenyl group having 2 to 8 carbon atoms, or R_1 and R_2 together represent 2 to 6
1,2,3-benzothiadiazole-4-, which represents a membered alkylene or alkenylene chain]
Carboxylic acid oxime ester. (9) 5-chloro-1,2,3-benzothiadiazole-4-carboxylic acid acetoxime ester according to claim 8. (10) Following formula II ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, Hal represents a halogen atom, and X is claim 1
1,2,3-benzothiadiazole-4- represented by
A carboxylic acid derivative is prepared by the following formula in an inert solvent in the presence of a base.
III H-A (III) [In the formula, A represents the meaning defined in claim 1] The following formula I ▲Mathematical formula, chemical formula, table, etc. 1,2,3-benzothiadiazole-4- represented by ▼(I) [wherein A and X represent the meanings defined in claim 1]
A method for producing a carboxylic acid derivative. (11) Following formula VII ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ (VII) [In the formula, X and R represent the meanings defined in claim 1, and E is a hydrogen atom, methyl group, ethyl group, isopropyl 2-amino-3-mercaptobenzoic acid represented by 2-amino-3-mercaptobenzoic acid represented by 2-amino-3-mercaptobenzoic acid is an alkali metal nitrate at a temperature of -20° to 30°C in an acid medium. 1,2 expressed by the following formula I c ▲ Numerical formula, chemical formula, table, etc. ▼ (I c) [In the formula, R and X represent the meanings defined in claim 1] ,3-benzothiadiazole-4-
The carboxylic acid ester is isolated or this ester is prepared in an aqueous solution in the presence of an inorganic base using the following formula I f ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I f) [In the formula, X is in claim 1 1,2,3-benzothiadiazole-4- represented by
Saponification to a carboxylic acid, and this acid in an inert organic solvent,
After treatment with a halogenating agent, the following formula II ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, X represents the meaning defined in claim 1, Ha
l represents a halogen atom] An acid halide represented by the following formula III H-A (III) is produced in an inert organic solvent in the presence of a base [wherein X is defined in claim 1] A method for producing a 1,2,3-benzothiadiazole-4-carboxylic acid derivative represented by the formula I according to claim 1, characterized in that the alcohol, thiol or oxime represented by the following formula is reacted. (12) The active ingredient is 1, 2, 3- expressed by the following formula I ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, A and X represent the meanings defined in claim 1] Benzothiadiazole-4-
A plant growth regulating composition comprising an effective amount of a carboxylic acid derivative together with an inert carrier material. (13) A plant, a plant part, or a seed according to claim 1.
, 2,3-benzothiadiazole-4-carboxylic acid derivative, or a composition comprising such a compound. (14) The method of claim 13 for inhibiting plant growth in sugarcane, cereal, corn, fruit, rice and soybean crops or in cover crops. (15) The method of claim 13 for controlling plant growth to improve lodging resistance and increase yield in soybeans. (16) The following formula II as an intermediate ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, X represents the meaning defined in claim 1, Ha
l represents a halogen atom] 1,2,3-benzothiadiazole-4-
Carboxylic acid halide. (17) Following formula VII ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VII) [In the formula, R and X represent the meanings defined in claim 1, and E is a hydrogen atom, methyl group, ethyl group, isopropyl 2-amino-3-mercaptobenzoic acid derivative represented by: (18) The following formula V ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) [In the formula, R and X represent the meanings defined in claim 1, and Hal represents a halogen atom] 3- a halo-2-nitro-benzoic acid derivative in an inert organic solvent;
Reaction with a mercaptan of the following formula IX HS-E (IX) [wherein E represents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, a dodecyl group, or a benzyl group] in the presence of an equimolar amount of a base. and the following equation V
I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (VI) [In the formula, R and X represent the meanings defined in claim 1, and E is a hydrogen atom, methyl group, ethyl group, isopropyl group, dodecyl group, or 18. The formula according to claim 17, which comprises reducing 3-mercapto-2-nitro-benzoic acid represented by [representing a benzyl group] to the corresponding 2-amino-3-mercapto-benzoic acid derivative with a reducing agent.
A method for producing a 2-amino-3-mercapto-benzoic acid derivative represented by VII. (19) The following formula VI as an intermediate ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (VI) (In the formula, R and X represent the meanings defined in claim 1, and E is a hydrogen atom, a methyl group, ethyl group, isopropyl group, dodecyl group or benzyl group] A 3-mercapto-2-nitrobenzoic acid derivative represented by: